Reaction product of aldehydes and triazine derivatives



Patented Mar. 2, 1943 REACTION PRODUCT OF ALDE'HYDES AND TRIAZINEDERIVATIVES Gaetano F. D'Alelio, Pittsfield, Mass, assignor to GeneralElectric Company, a corporation of New York No Drawing. ApplicationDecember 24, 1941,

' Serial No. 424,330

20 Claims.

This invention relates to the production of new synthetic materials andmore particularly to new reaction products of particular utility in theplastics and coating arts. Specifically the invention is concerned withcompositions of matter comprising a condensation product of ingredientscomprising an aldehyde, including polymeric aldehydes andaldehyde-addition products, e. 8.. formaldehyde, para-formaldehyde,dimethylol invention into effect are triazine derivatives correspondingto the general formulas mm A a. trimethyloi melamine, etc., and atriazine and, more particular y,

derivative corresponding to the following General formula: rum 0 w N iRnN-o cso..R,.-d-NR-Y0n In the above formula n represents an integer andis at least 1 and not more than 2, Z represents a memberoi the classconsisting of oxygen and sulfur, Y represents a divalent carbocyclicradical, and R represents a member 0! the class consisting of hydrogenand monovalent hydrocarbon and substituted hydrocarbon radicals, moreparticularly halo-hydrocarbon radicals. Since n represents an integerwhich is 1 or 2, it will be seen that the linkage of thehydroxycarbocyclic-carbamyl-alkyl orhydroxycarbocyclicthiocarbamyl-alkyl grouping to the sulfur atom in allcases will be alpha or beta to the hydroxycarbocyclic-carbamyl or-thiocarbamyl grouping. It also will be observed that linkage of thetriazinyl grouping to the sulfur atom is through a carbon atom. a

Illustrative examples of radicals that R in the above formula mayrepresent are: aliphatic (e. g., methyl, ethyl, propyl, isopropyl,allyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl, hexyl,etc.) including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl,cyclohexyl, cyclohexenyl, cycloheptyl, etc); aryl (e. g., phenyl,diphenyl or xenyl, naphthyl, etc.); aliphatic-substituted aryl (e. g.,tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl,z-butenylphenyl, tertiary-butylphenyl, etc.) aryl-substituted allphatic(e. g., benzyl, phenylethyl, phenylisopropyl, cinnamyl, etc.); and theirhomologues, as well as those groom with one or more of their hydrogenatoms substituted by, for example, a

halogen. Specific examples of halogeno-substituted hydrocarbon radicalsare chloromethyi, chloroethyl,'chlorophenyl, dichlorophengl,ehlorocyclohexyl, ethyl chlorophenyl, phenyl chloroethyl, bromoethyl,bromopropyl, bromotolyl, etc.

Preferably R in Formula I is hydrogen. Also especially suitable for usein carrying the present III where n, Z, Y and B. have the same meaningsas above given with reference to Formula I.

Illustrative examples oi divalent carbocyclic radicals that Yin FormulasI, II and 111 may represent are: divalent aryl, e. g., phenylene,xenylene, naphthylene, etc.; divalent aliphatic-aryl, e. g.,2,5-tolylene, para-(2,3-l lylene), etc.; divalent cycloaliphatic, e.g.,.cyclopentylene, cyclohexylene, cyclopentenylene, cyclohexenylene,cycloheptylene, etc.; and their homologues, as well as those divalentcarbocyclic radicals with one or more of their hydrogen atoms replacedby a sub stituent, e. g., halogeno, amino, acetyl, acetoxy, carbalkoxy,alkoxy, aryloxy, sulfamyl, alkyl, a1- kenyl, a hydroxy group or groups-in addition to the single ---OH group shown in the above formulas, etc.Specific examples of substituted divalent carbocyclic radicals arechlorophenylene, bromophenylene, chloronaphthylene, bromo naphthylene,bromo 2,5-tolylene, chlorocyclopentylene, chlorocyclopentenylene,carbomethoxyphenylene, ethoxyphenylene, acetophenylene,acetoxyphenylene, bromocyclopentylene, amino phenylene,phenoxyphenylene, suliamylphenylene, methylphenylene (tolylene),allylphenylene, etc. Preferably Y is phenylene or methylphenylene.

Instead of the symmetrical triazines (s-triazines) represented by theabove formulas, corresponding derivatives oi the asymmetrical triazinesor of the vicinai triazines may be used. Also, instead of the triazinyimonosulfldes represented by the above formulas, the dior trisulfldes ofthe triazines (symmetrical, asymmetrical or vicinal) may be employed.

The trlazine derivatives that are used in carrying the present inventioninto effect are more fully described and claimed in my copendingapplication Serial No. 423,691, filed December 19, 1941, and assigned tothe same assignee as the pr sent invention. As pointed out in thiscopending application. a suitable method of pre paring the triazinederivatives employed in practicing the present invention compriseseffecting reaction between a mercapto diamino symmetrical triazine(s-triazine) and a hydroxycarbocyclic carbamyl alkyl halide (or ahydroxycarbocyclic-thiocarbamyl-alkyl halide) in the presence of ahydrohalide acceptor, e. g., an alkali-metal hydroxide. When thestarting components, proportions thereof and reaction conditions aresuch that the hydrogen atom of the -OH group of the hydroxycarbocycliccompound is replaced by the residue of the hydrohalide acceptor, e. g.,by an alkali metal, the hydroxy compound desired as a final product isobtained by treating this intermediate product with hydrochloric;hydrobromic, sulfuric or other suitable organic or inorganic acid in anamount just sutflcient to form the desired hydroxy derivative.

Specific examples of triazinyl hydroxycarbocycllc-carbamyl-alkylsulfides and triazinyl hydroxycarbocyclic-thiocarbamyl-alkyl sulfidesthat may be used in producing my new condensation products are listedbelow:

The diamino s-triazinyl ortho-, metaandparahydroxyphenyl-carbamyl-methyl sulfides The diamino s-triazinylortho-, metaand parahydroxyphenyl-thiocarbamyl-methyl sulfides Thediamino s-trazinyl ortho-, metaand parahydroxytolyl-carbamyl-methylsulfides The diamino s-triazinyl ortho-, metaand parahydroxytolyl-thiocarbamyl-methyl sulfides The 4,6-di-(methylamino)s-triazinyl ortho-,

metaand para hydroxyphenyl carbamylmethyl sulfides The4,6-di-(ethylamino) s-triazinyl ortho-, metaandpara-hydroxyphenyl-thiocarbamyl-methyl sulfides The 4,6-di-(ar 1i1ino)s-triazinyl ortho-, metaand para-hydroxytolyl-carbamyl-rnethyl sulfldesThe 4,6-di-(cyclohexylamino) s-triazinyl ortho-,

metaand para hydroxytolyl thiocarbamylmethyl sulfides The diaminos-triazinyl alpha-(ortho-, metaand para-hydroxyphenyl-carbamyl-ethyl)sulfides The diamino s-triazlnyl beta-(ortho-, metaandpara-hydroxyphenyl-carbamyl-ethyl) sulfides The diamino s-triazinylalpha-(ortho-, metaand para-hydroxyphenyl-thiocarbamyl-ethyl) sul fidesThe diamino s-triazinyl beta- (ortho metaandpara-hydroxyphenyl-thiocarbamyl-ethyl) sulfides The diamino s-triazinylalpha-(ortho-, metaand para-hydroxytolyl carbamyl-ethyl) sulfides Thediamino s-triazinyi beta-(ortho-, metaand para-hydroxytolylcarbamyl-ethyl) sulfides The diamino s-triazinyl alpha- (ortho-, metaandpara-hydroxytolyl thiocarbamyl-ethyl) sulfides The diamino s-triazinylbeta-(ortho-, meta and para-hydroxytolyl thiocarbamyl-ethyl) sulfidesThe 4,6-di-(methylamino) s-triazinyl-2 alpha- (ortho-, metaandpara-hydroxyphenyl carbamyl-ethyl) sulfides The 4,6 di-(propylamino)s-triazinyl-2 beta (ortho-, metaand para-hydroxyphenyl carbamyl-ethyl)sulfides The 4,6-di-ianilino) s-triazinyl-Z alpha-(ortho-,

metaand para-hydroxytolyl-carbamyl ethyl) sulfides The 4,6 di(cycloheptylamino) s triazinyl 2 beta-(ortho-, meta andpara-hydroxytolyl-carbamyl-ethyl) sulfides The 4,6 di-(ethylamino)s-triazinyl-Z alpha- (ortho-, metaandpara-hydroxyphenyl-thiocarbamyl-ethyl) sulfides 4-ethylamino G-aminos-triazinyl-2 alpha-(parahydroxyphenyl-carbamyl-pentyl) sulfide4-(3'-butenylamino) fi-methylamino s-triazinyl- 2 hydroxyphenyl carbamyl(phenyl) -methyl sulfide 4 cyclohexenylamino 6 naphthylamino 5 triazinyl2 para hydroxyphenyl (chloroethyl) carbamyl-methyl sulfide4-chlorocyclopentylamino 6-toluido s-triazinyl2 hydroxycyclohexyl-(phenyl) carbamyl-methyl sulfide 4-bromoto1uido 6-benzylaminos-triazinyl-Z hydroxycyclopentyl-carbamyl- (tolyl) -methyl sulflde I4,6-di-(iodophenylamino) s-triazinyl-Z hydroxyphenyl-carbamyl-methylsulfide 4-amino G-fiuorotoluido s-triazlnyl-2hydroxytolyl-carbamyl-methyl sulfide Additional examples of triazinederivatives that may be employed in producing the new condensationproducts of the present invention are given in my above-identifiedcopending' application Serial No. 423,691.

The present invention is based on my discovery that new and valuablematerials of particular utility in the plastics and coating arts can beproduced by effecting reaction between ingredients comprisingessentially an aldehyde, including polymeric aldehydes andaldehyde-addition products, and certain triazinylhydroxycarbocyclic-carbamyl (or thiocarbamyl) -alkyl sulfides, numerousexamples of which have been given above and in the above-identifiedcopending appllcation.

Resins heretofore have been made by condensing an aldehyde with certainthioammelin resinous condensation products of an aldehydeand thethioammeline ethers heretofore used.

Resins also have been made heretofore by condensing an aldehyde, e. g.,formaldehyde, with a hydroxycarbocyclic. compound, e. g., a phenol. Thewell-known phenol-aldehyde synthetic resins are typical examples of suchcondensation products. Although these resins have a wide field ofutility, there are many applications for which they are unsuited, forinstance where lightness of color or high are resistance are desired.The

resins of the present invention combine in one I product the desirableproperties of the phenolaldehyde condensation products, while at thesame time providing a material of more desirable properties, e. g.,improved color and higher are resistance, than the phenol-aldehyderesins.

In carrying my invention into effect the initial asiaroa condensationreaction may be carried out at normal or at elevated temperatures, atatmospheric, sub-atmospheric or super-atmospheric pressures, and underneutral, alkaline or acid conditions. Preferably the reaction betweenthe components is initiated under alkaline conditions.

Any substance yielding an alkaline or an acid aqueous solution may beused in obtaining alkaline or acid conditions for the initialcondensation reaction. For example, I. may use an alkaline substancesuch as sodium, potassium or calcium hydroxides, sodium or potassiumcarbonates,

mono-, dior tri-amines, etc. In some cases it is desirable to cause theinitial condensation reaction between the components to take place inthe presence of a primary condensation catalyst and a secondarycondensation catalyst. The primary catalyst advantageously is either analdehyde-non-reactable nitrogeni-containing basic tertiary compound, e.g., tertiary amines such as trialkyl (e. g., trimethyl, triethyl, etc.)amines, triaryl (e. g., triphenyl, tritolyl, etc.) amines, etc., or analdehyde-reactable nitrogen-containing basic compound, for instanceammonia, primary amines (e. a, ethyl amine, propyl amine, etc.) andsecondary amines (e. g., dipropyl amine, dibutyl amine, etc.). Thesecondary condensation catalyst, which ordinarily is used in an amountless than the amount of the primary catalyst, advantageously is a fixedalkali, for instance a carbonate, cyanide or hydroxide of an alkalimetal (e. g., sodium, potassium, lithium, etc.)

Illustrative examples of acid condensation catalysts that may beemployed are inorganic or organic acids such as hydrochloric, sulfuric,phosphoric, acetic, lactic, acrylic, malonic, etc., or acid salts suchas sodium acid sulfate, monosodium phosphate, monosodium ph thalate,etc. Mixtures of acids, of acid salts or of acids and of acid salts maybe employed if desired.

The reaction between the aldehyde, e. g., formaldehyde, and the triazinederivative may be carried out in the presence of solvents or diluents,fillers, other natural or synthetic resinous bodies, or while admixedwith other materials that also can react with the aldehydic reactant orwith the triazine derivative, e. g., ketones, urea (NHzCONHz), thiourea,selenourea, iminourea (guanidine) substituted ureas, thioureas,selenoureas and iminoureas, numerous examples of which are given invarious copending applica-- tions of mine, for instance in my copendingapplication Serial No. 363,037, filed October 26, 1940; monoamides ofmonocarboxylic and polycarboxylic acids and polyamides of polycarboxylicacids, e. g., acetam de, halogenated acetamides (e. g., a chlorinatedacetamide), malelc monoamide, malonic monoamide, phthalic monoamide,

maleic diamide, fumaric diamide, malonic diamide, itaconic diamide,succinic diamide, phthalic diamide, the monoarnide, diamide and triamideof tricarballylic acid, etc.; aldehydereactable triazines other than thetrinzine derivatives constituting the primary components of the resinsof the present invention, e. on, male-- mine, ammeline, ammelide, melem,melam, melon, numerous other examples being given in various copendingapplications of mine, for instance in application Serial No. 377,524,filed February 5, 1941, and in applications referred to in saidcopending application; phenol and substituted phenols, e. g., thecresols, the xylenols, the tertiary alkyl phenols and other phenols suchas mentioned in my Patent No. 2,239,541; mpno= hydric and polyhydricalcohols, e. an, butyl alco- 1101, amyl alcohol, ethylene glycol,glycerine, poly vinyl alcohol, etc; amines, including aromatic amines,e. g., aniline, etc.; and the like.

The modifying reactants may be incorporated with the triazine derivativeand the aldehyde by mixing all the reactants and efiecting condensationtherebetween or by various permutations oi reactants as described, forexample, in my copending application Serial No. 363,037 with particularreference to reactions involving a urea, en aldehyde and a semi-amide ofoxalic acid. For instance, I may form a partial condensation product ofingredients comprising (1) urea or melamine or urea and melamine, (2) atriazlne derivative of the kind herein described (for example, a diaminos-triazinyl ortho-, metaor para-hydroxyphenyl-carbamyl-methyl sulfide,a,

diamino s-triazinyl ortho-, metaor para-hydroxytolyl-carbamyl-methylsulfide, etc.) and (3) an aldehyde, including polymeric aldehydes andaldehyde-addition products, for instance formaldehyde, paraformaldehyde,dimethylol urea, a polymethylol melamine, e, g., hexamethylol melamine,etc., and thereafter efiect reaction between this partial condensationproduct and, for example, a curing reactant, specifically a chlorinatedacetamide, to obtain a heat-curable composition.

Some of the condensation products of this invention are thermoplasticmaterials even at an advanced stage of condensation, while others arethermosetting or potentially thermosetting bodies that convert underheat or under heat and pressure to an insoluble, infusible state. Thethermo plastic condensation products are of particular value asplasticizers for other synthetic resins. The thermosetting orpotentially thennosettina' condensation products, alone or mixed withfill ers, pigments, dyes, lubricants, plasticizers, curing agents, etc.,may be used, for example, in the production of molding compositions.

The heat-curable resinous condensation products of this invention showexcellent flow characteristics during a short curing cycle. This is aproperty that is particularly desirable in a molding compound. Themolded articles have a high dielectric strength and excellent resistanceto arcing. They have a good surface finish and, in general, are betterthan the ordinary urea-formaldehyde resins in resistance to water.

Depending upon the particular conditions of reaction and the particularreactants employed, the intermediate or partial condensation productsvary from clear, colorless or colored, syrupy, water-soluble liquids toviscous, milky dispersions and gel-like masses of decreased solubilityin ordinary solvents, e. g., alcohol, dioxane, Cellosolve, ethyleneglycol, glycerine, etc. These liquid intermediate condensation productsmay be concentrated or diluted further by the removal or addition ofvolatile solvents to form liquid coating compositions of adjustedviscosity and concentrations. The heat-convertible or potentiallyheatconvertible resinous condensation products may be used in liquidstate, for instance as surface coating materials, in the production ofpaints, varnishes, lacquers, enamels, etc., for general adhesiveapplications, in producing laminated articles and for numerous otherpurposes. The liquid heat-hardenable or potentially heathardenablecondensation products also may be used directly as casting resins, whilethose which are of a gel-like nature in partially condensed state may bedried and granulated to form clear unfilled heat-convertible resins.

In order that those skilled in the art better may understand how thisinvention may be carried into effect, the following examples are givenby way of illustration. All parts are by weight.

Example 1 Parts Diamino s-triazinyl para-hydroxyphenylcarbamyl-methylsulfide (4,6-diamino striazinyl-Z para hydroxyphenyl carbamyl-methylsulfide; 2,6-diamino s-triazinyl-4 para-hydroxyphenyl-carbamylmethylsulfide; 2,4-diamino s-triazinyl-6 para hydroxyphenyl carbamyl methylsulfide) 29.2 Aqueous formaldehyde (approx. 37.1

HCHO) 48.6 Aqueous ammonia (approx. 28% NI-h) 1.5 Aqueous solution ofsodium hydroxide (0.5 N) 1.0 Water-; 40.0 Chloroacetamide(monochloroacetamide) 0.3

resulting syrup was mixed with 27 parts alpha cellulose in flock formand 0.1 part of a mold lubricant, specifically zinc stearate, to form amolding (moldable) compound. The wet molding composition was dried atroom temperature-until sufficient moisture had been removed to yield acompound that could be molded satisfactorily. A sample of the dried andfinely ground molding compound was molded (into the form of a disk) forminutes at 140 C. under a pressure 01' 5,600 pounds per square inch. Themolded piece was extracted hot from the mold and, upon cooling to roomtemperature, did not become distorted. It was well cured throughout andhad a well-knit and homogeneous structure. The molding compound showedgood plastic flow during molding. The molded disk was tested for itswater-resistance characteristics by immersing it in boiling water for 15minutes, followed by immersion in cold water for 5 minutes. It absorbedonly 4.9%

by weight of water on this accelerated test.

Example 2 Example 1 was repeated using diamino s-t'ri azinyl orthohydroxyphenyl carbamyl methyl sulfide in place of the corresponding paracompound. The molding composition of this example was molded into theform of a disk, using a molding time of 5 minutes, a temperature of 140C. and a pressure oi 6,750 pounds per square inch. The molded productwas white in color, as compared with the yellowish, brownish or reddishpieces obtained when similar compositions are prepared utilizing theordinary phenol-formaldehyde resins. throughout. It absorbed only 3.46%by weight of water when tested for its water resistance as describedunder Example 1.

Instead of using chloroacetamide in accelerating the curing of thepotentially reactive resinous material (Examples 1 and 2 and subsequentex amples), heat-convertible compositions may be produced by adding tothe partial condensation product (in syrupy or other form) direct oractive, curing catalysts (e. g., citric acid, phthalic an- The moldedpiece was well curedhydride, malonic acid, oxalic acid, etc.) or latentcuring catalysts (e. g., sodium chloroacetate, N- diethylchloroacetamide, glycine ethyl ester hydrochloride, etc.), or byintercondensation with curing reactants other than monochloroacetamide(e. g., diand tri-chloroacetamides, chloroacetonitriles, alpha betadibromopropionitrile, aminoacetamide hydrochloride, ethylene diaminemonohydrochloride, the ethanolamine hydrochlorides, nitrourea,chloroacetyl urea, chloroacetone, glycine, sulfamic acid, citricdiamide, phenacyl chloride, etc). Other examples of active and latentcuring catalysts and of curing reactants that may be employed toaccelerate or to eflect the curing of the thermosetting or potentiallythermosetting resins of these and other examples are given in variouscopending applications of mine, for instance in 'copending applicationsSerial No. 346,962, filed July 23, 1940, and Serial No. 354,395, filedAugust 27, 1940, both of which applications are assigned to the sameassignee as the present invention.

Example 3 Parts Diamino s-triazinyl ortho-hydroxyphenylcarbamyl-methylsulfide 14.6 Urea 30.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 89.1 Aqueous solution of sodium hydroxide 0.5 N) 2.0 Aqueousammonia (approx. 28% NH3) 3.5 Chloroacetamide All of the abovecomponents with the exception of the chloroacetamide were heatedtogether under reflux at the boiling temperature of the mass ior lfiminutes. The chloroacetamide was now added and refluxing was continuedfor an additional 5 minutes. The resulting partial condensation. productwas mixed with 49.5 parts alpha cellulose in flock form and 0.3 partzinc stearate to form a molding compound. The wet compound was dried forabout 16 hours at room Example 4 Parts Diamino s-triazinylpara-hydroxyphenylcarbamyl-methyl sulfide 14.6 Melamine 37.8 Aqueousformaldehyde approx. 37.1

HCHO) i 97.2

Aqueous solution of sodium hydroxide (0.5 N) 2.5 Aqueous ammonia(approx. 28% NH3) 2.0 Chloroacetamide 0.3

All of the above ingredients with the exception of the chloroacetamidewere heated together under reflux at the boiling temperature of the massfor 10 minutes. The chloroacetamide was now added and refluxing wascontinued for an additional 1 minute. A molding compound was made fromthe resulting resinous syrup by mixing are Example Parts Diaminos-triazinyl ortho-hydroxyphenylcarbamyl-methyl sulfide 29.2Sulianilamide 17.2

Aqueous formaldehyde (approx. 37.1%

HCHO) 48.6

Aqueous solution of sodium hydroxide (0.5 N) 2.0 Water 20.0Chloroacetamlde 0.4

All of the above components with the exception of the chloroacetan idewere heated together under reflux at boiling temperature for 4 minutes.(At the end of this time the mass had separated into two layers.) Thechloroacetamide was now added and refluxing was continued for anadditional 2 minutes. The resulting resinous syrup was mixed with 32.5parts alpha cellulose and 0.2 part zinc stearate to form a moldingcompound. The wet composition was dried at room temperaobtained time forabout 16 hours. A sample of the dried and ground molding compound wasmolded for 5 minutes at 1t0 C. under a pressure or 2,000 pounds persquare inch. A well-cured molded piece'that was well knitted togetherinto a ho mogeneous structure was obtained. The molded piece had verygood water resistance. as shown by the fact that it ahsorloed only"1.08% by weight I of water when tested as described under Example 1. Themolded article also had ample flash when it was removed rrom the mold,indicating that the plastic flow during molding was satisfactory.

Example 6 Parts Dia s triazlnyl para hydroxyphenylcarbamyl-methylsulfide 14.0

Dimethylol urea (commercial grade contaming approx. 11% by weight ofwater)- 00.0

Water i 00.0

Aqueous solution oi sodium hydroxide (0.5

, 2.0 Aqueous onia (approx. 28% Krishna- 3.0 Chloroacetamide as All ofthe above components with the excep tlon oi the chloroacetamide wereheated tosether under reflux at boiling temperature for I 23 minutes.The chloroacetamlde was now add- 1. The piece was extracted hot from themold and did not become distorted upon cooling to room temperature. Itsplastic flow during molding was very good.

After heating together all of the above components with the exception ofthe chloroacetamide under reflux at boiling temperature for 7 minutes.the chloroacetamide was added and the resulting syrup immediately wasmixed with 31.1 parts alpha cellulose and 0.2 part zinc stearate. Thewet molding compound thereby was dried at room temperature for about 16hours. A well-cured, well-knit molded disk having a homogeneousstructure was produced by molding a sample of the dried and finelyground compound for 5 minutes at 140 C. under a pressure of 5,600 poundsper square inch. The molded piece had exceptionally high waterresistance, as shown by the fact that it absorbed only 0.23% by weightof water when tested as described under Example 1. The molding compoundshowed good plastic flow during molding.

Example 8 Parts 'Diamino s-triazinyl ortho-hydroxyphenylcarbamybmethylsulfide 87.6 Furfural 196.0

. was heated on a 140 C. hot plate. The addition of glycine, phthalicmonoamide, aminoacetamide hydrochloride, phenacyl chloride and othercuronly rear. by weight or water whm tested for its water resistance asdescribed under pic 20 log agents such as mentioned hereinbeforeaccelerated the conversion of the resin to an in soluble and iniusiblestate when the individual samples containing the curing agent wereheated on a C. hot plate. The cured resin possessed excellent adhesiveand cohesive characteristics. The resinous composition of this exampleis especially suitable for me" compounds.

Eeample 9 Example 8 was repeated using diamlno s-triazinylpara-hydyroxyphenyl carbamyl methyl sulfide instead of the correspondingortho compound. The resulting resin had properties much the same as theproduct of Example 8 with the exception that the cured resin was lessadhesive than the cured resin of Example 8.

Example 10 Parts Diamlno s-triazlnyl ortho-hydroxyphenyl the productionof mold-' weremixed (the acrolein being added last) and heated togetherunder reflux at boiling temperature for 20 minutes. When a sample of theresulting resin was heated on a140 C.-hot plate, it hardened in about 2minutes. When glycine, phenacyl chloride, phthalic monoamide,aminoacetamide hydrochloride, chloroacetamide and other curing agentssuch as mentioned hereinbefore were added to the resin, the modifiedresin set to an infusible mass in less than 2% minutes when theindividual sample was heated on a 140 C. hot plate. The cured resinshowed excellent cohesive characteristics. The product of this examplemay be used in the production of laminating varnishes and moldingcompositions.

Aqueous solution of sodium hydroxide (0.5

were heated together under reflux at boiling temperature for minutes,yielding a clear'syrup. This syrup was dehydrated. The dehydrated,syrupy resin was soluble in ethyl alcohol, ethylene glycol, Cellosolve,benzyl alcohol, butyl alcohol and dioxane. When a sample of thedehydrated syrup containing a curing agent, specifically hydrochloricacid, was applied to a glass plate and the coated plate was baked forabout 16 hours at 80 C., a hard, transparent, waterwhite,water=resistant, smooth, adhering film was formed on the plate. When thecuring agent was omitted, the film was slightly softer and lessresistant to water. The resinous composition of this example isespecially suitable for use in the production of lacquers, enamels,varnishes and other surface-protective coating compositions.

Aqueous solution of sodium hydroxide (0.5 N)

were heated together under refluxat the boiling temperature of the massfor 13 minutes, yielding a clear resinous syrup. When a sample of thissyrup was heated on a 140 C. hot plate, it set to a rubbery, uncuredmass in less than 2 minutes. However, the addition of glycine,aminoacetamide hydrochloride, chloroacetamide and other curing agentssuch as hereinbefore mentioned, followed by heating on a 140 C. hotplate,

caused the resin to cure rapidly to an infusible.

state. The resinous compositions to which ouring agents had been .addedtherefore would be suitable for use in the manufacture of laminatingvarnishes and molding compounds. The resin initially obtained, that is,prior to the addition of the curing-agent, may be used as a modifierof.other synthetic resins. For example, it may be used as a modifier ofrapidly curing amipoplasts to control their flow characteristics.

or plasticity Example 13 Parts Diamino s-triazinyiortho-hydroxyphenylcarbamyl-methyl sulfide 43.6 Diethylmalonate 24.0

Aqueous formaldehyde (approx. 37.1%

HCHO) 121.0

Aqueous solution of sodium hydroxide were heated together under refluxat the boiling temperature of the mass for 30 minutes. When a sample ofthe resulting syrupy condensation product was heated on a 140 C. hotplate, a soft thermoplastic resin was obtained. The thermoplasticity ofthe resin appeared to be unchanged by the addition of curing agents suchas hereinbefore mentioned. The dehydrated syrupy resin was soluble inethyl alcohol, dioxane, butyl alcohol, ethylene glycol, etc. Theresinous material of this example is especially suitable for use as aplasticizer in molding compounds and coating compositions where productsof improved fiow characteristics are desired.

Example 14 Parts Diamino s-triazinyl para-hydroxyphenylcarbamyl-methylsulfide 43.6 Glycerine 13.8 Aqueous formaldehyde (approx. 37.1%

HCHO) 121.0 Aqueous sodium hydroxide solution were heated together underreflux at the boiling temperature of the mass for 17 minutes. Theresinified syrup was dehydrated. The dehydrated syrup was soluble inethyl alcohol, Cellosolve, butyl alcohol, dioxane, ethylene glycol andother solvents. Samples of the soluble resin, with and without a curingagent, were applied to glass plates and the coated plates were baked inan oven at C. for several hours. In all cases the baked films wereexceptionally hard, water-clear, smooth, glossy, very resistant to waterand tightly adhering to the glass surface. The solubility andfilm-forming characteristics of the resinous material of this examplemake it especially suitable for use in the production of spirit andbaking varnishes and other liquid coating compositions. It may be usedas a modifier of varnishes of the aminoplast and alkyd-resin types.

Example 15 Parts Diamino s-triazinyl ortho-hydroxyphenyi-,

carbamyl-methyl sulfide 43.6

Polyvinyl alcohol 6.6 Aqueous formaldehyde (approx. 37.1% HCHO) 121.0Water 110.0

Aqueous solution of sodium hydroxide drawn into continuous filamentsthree to four feet long without breaking. No effort, was made to obtainlonger filaments by controlling the drawing conditions.

When a glass plate was coated with a sample of the resin and the coatedplate was baked at 80 C. for several hours, a very. hard, smooth,adhering, water-resistant film was formed on the plate. In the absenceof a curing agent, the film was transparent; but when a curing agent, e.g., hydrochloric acid, was present the film was translucent.

The resinous material of this example, with no added curing agentpresent, is suitable for use in the production of fiber-formingcompositions and coating materials. When curing agents such ashereinbefore have been mentioned are incorporated into the syrupy ordehydrated resin, the resulting product may be used in the preparationof molding compounds, various coating compositions such as varnishes,lacquers, enamels, etc., and for numerous other purposes.

Itwill be understood, of course, by those skilled in the art that thereaction between the aldehyde and the triazine derivative may beeffected at temperatures ranging, for example, from room temperature tothe fusion or boiling temperatures of the mixed reactants or ofsolutions of the mixed reactants, the reaction proceeding more slowly atnormal temperatures than at elevated temperatures in accordance with thegeneral laws of chemical reactions. Thus, instead of effecting reactionbetween the ingredients of the above examples at boiling temperatureunder reflux as mentioned in the various examples, the reaction betweenthe components may be carried out at temperatures ranging from roomtemperature to the boiling temperature using longer reaction periodsand, in some cases, stronger catalysts and higher catalystconcentrations.

It also will be understood by those skilled in the art that my inventionis not limited to condensation products obtained by reaction ofingredients comprising an aldehyde and the speciflc diamino s-triazinylhydroxycarbocycliccarbamyl-alkyl sulfides named in the aboveillus'trative examples. s-triazinyl ortho hydroxyphenyl carbamyl methylsulfide and diamino s-triazinyl para-hydroxyphenyl-carbamyl-methylsulfide mentioned in the aboxe examples, I may use diamino striazinylmeta-hydroxyphenyl-carbamyl-methylsulfide, the diamino s-triazinylhydroxytolylcarbamyl-methyl sulfides, or any other organic sulfide (ormixture thereof) of the kind with which this invention is concerned,numerous ex amples of which compounds have been given hereinbefore andin my copending application Serial No. 423,691.

In producing these new condensation products the choice of the aldehydeis dependent largely upon economic considerations and upon theparticular properties desired in the finished product. I prefer to useas the aldehydic reactant formaldehyde or compounds engenderingformaldehyde, e. g., paraformaldehyde, hexamethylene tetramine, etc.Illustrative examples of other aldehydes that may be used areacetaldehyde, propionaldehyde, butyraldehyde, methacrolein,crotonaldehyde, benzaldehyde, furfural, hydroxyaldehydes (e. g.,glycollic aldehyde, glyceraldehyde, etc.), mixtures thereof, or mixturesof formaldehyde (or compounds engendering formaldehyde) with suchaldehydes. Illustrative examples of aldehyde-addition products that maybe employed instead of the alde- Thus, instead of diamino hydesthemselves are the mono and poly-(N- carbinol) derivatives, moreparticularly the monoand poly-methylol derivatives of urea, thiourea,selenourea and iminourea, substituted ureas, selenoureas, thioureas andiminoureas (numerous examples of which are given in my copendingapplication Serial No. 377,524), monoand poly-(N-carbinol) derivativesof amides of poly-carboxylic acids, e. g., fumaric, adipic, malonic,succinic, citric, phthalic, etc., monoand poly-(Ncarbinol) derivativesof the aminotriazoles, monoand poly(N-carbinol) derivatives of theaminodiazines, etc. Particularly good results are obtained with activemethylene-containing bodies such as a methylol urea, moreparticularlymonoand di-methylol ureas, and a methylol melamine, e. g., monomethylolmelamine and polymethylol melamine (di-, tri-, tetra-, pentaandhexamethylol melamines). Mixtures of aldehydes and aldehyde-additionproducts may be employed, e. g., mixtures of formaldehyde and methylolcompounds such, for instance, as dimethylol urea, trimethylol melamine,hexamethylol melamine, etc.

The ratio of the aldehydic reactant to the triazine derivative may bevaried over a wide range depending upon the particular propertiesdesired in the final product. Ordinarily these reactants are employed inan amount corresponding to at least one mol of the aldehyde,specifically formaldehyde, for each mol of the triazine derivative.Thus, I may use, for example, from 1 to 8 or 9 mols of an aldehyde foreach mol of triazine derivative. When the aldehyde is avail able forreaction in the form of an alkylol derivative, more particularly amethylol derivative such, for instance, as dimethylol urea, trimethylolmelamine, etc., then higher amounts of such aldehyde-addition productsare used, for instance, from 2 or 3 up to 15 or 20 mols of such alkylolderivatives for each mol of the triazine derivative.

As indicated hereinbefore, and as further shown by a number of theexamples, the properties of the fundamental resins of this invention maybe varied widely by introducing other modifying bodies before, during orafter effecting condensation between the primary components. Thus, asmodifying agents I may use, for instance, monohydric alcohols such asethyl, propyl, isopropyl, isobutyl, hexyl, etc., alcohols; polyhydricalcohols such as diethylene glycol, triethylene glycol, pentaerythritol,etc.; amides such as formamide, stearamide, acryloamide, benz-. amide,toluene sulfonamides, benzene sulfonamides, adipic diamide, phthalamide,etc.; amines such as ethylene diamine, phenylene diamine, etc.; ketones,including halogenated ketones; nitriles, including halogenated nitriles,"I e. g., acrylonitrile, methacrylonitrile, succinonitrile,chloroacetonitriles, etc.; acylated ureasf more particularly halogenatedacylated ureas of the kind described, for example, in my copendjiingapplications Serial No. 289,273, filed Auguit 9, 1939, now Patent No.2,281,559, issued MayiiS; 1942, and Serial No. 400,649, filed July 1,19M; and others.

The modifying bodies also may take the form of high molecular weightbodies with or without resinous characteristics, for example, hydrolyzedwood products, formalized cellulose derivatives,

lignin, protein-aldehyde condensation products,'

condensation products of an aldehyde-reactable maleic, itaconic, I

wood flour, glass fibers, asbestoaincludingdefibrated asbestos, mineralwool; mica, cloth cuttings, etc.) may be compounded with the resin inaccordance with conventional practice to provide variousthermoplasticand 'thermosetting molding compositions.

The modified or unmodified resinous compositions of this invention havea'wide variety of uses. the production of molding compositions, they maybe used as modifiers of other. natural and synthetic resins, aslaminating varnishes m the production-0f laminated articles whereinsheet materials, e. g., paper, cloth, sheet asbestos, etc., are coatedand impregnated with the resin, superimposed and thereafter united underheat and pressure. They may be used in the production of wire or bakingenamels from which insulated wires. and other coated products are made,for bonding or cementing together mica flakes to form a laminated micaarticle, iorbonding to gether abrasive grains in the production ofresinbonded abrasive articles such, for instance, as grindstones,sandpapers, etc, in the manufacture of electrical resistors, etc. Theyalso may be employed for treating cotton, linen and other cellulosicmaterials in sheet or other form. They also may be used as impregnants'for electrical coils and for other electrically insulating applications.What I claim as new and desire to secure by Letters Patent of the UnitedStates is:

l. A composition of matter comprising the reaction product ofingredients comprising an aidehyde and a compound corresponding to thegene cral formula 4 where n represents an integer and is at least 1 andnot more than 2, Z represents a member 0! the class'consistins oi oxygenand sulfur, Y rep- For example, in addition to their use in aproposdehyde and a compound corresponding to the general formula hydrocarbonradicals.

5. A heat-curable resinous composition comprising a heat-convertiblecondensation product of ingredients comprising formaldehyde and acompound corresponding to the general formula NHR where Y represents adivalent carbocyclic radical and R represents a member of the classconsisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbonradicals.

6. A product comprising the heat-cured resinous composition of claim 5.

7. A resinous composition comprising the product of reaction ofingredients comprising an aldehyde and a diamino s-trlazinylhydroxycarbocyclic-carbamybmethyl sulfide.

resents a divalent carbocyclic radical, and R represents a member'oi theclass consisting of hydrogen and monovalent hydrocarbon andhalohydrocarbon radicals.

2. A composition as in claim 1 wherein the alwhere n represents aninteger and is at least 1 and not more than 2, Z represents a member ofthe class consisting or oxygen and sulfur, Y represents a divalentcarbocyclic radical, and R represents a member of the class consistingof hydrogen and monovalent hydrocarbon and halohydrocarbon radicals.

11. A composition as in claim 10 wherein the urea component is thecompound corresponding to the formula NHaCONHa and the aldehyde isiormaldehyde.

12. A heat-curable composition comprising the heat-convertible resinousreaction product of (l) a partlalcondensation product of ingredientscomprising formaldehyde and a diamino s-triazinylhydroxycarbocyclic-carbamyl-methyl sul iide, and (2) a curing reactant;

13. Aresinous composition as in claim 12 wherein the curing reactant isa chlorinated action product of ingredients comprising an al 7'acetamide,

14. A product comprising the heat-cured composition of claim 12.

15. A composition comprising the product of reaction of ingredientscomprising urea, formaldehyde and a diamino s-triazinylhydroxyphenylcarbamyl-methyl sulfide.

16. A" composition comprising the product of reaction of ingredientscomprising a methylol urea and a diamino s-triazinylhydroxyphenylcarbamyl-methyl sulfide.

17. A composition comprising the product of reaction of ingredientscomprising a polymethylol melamine and a diamino s-triazinylhydroxyphenyl-ca'rbamyl-methyl sulfide.

18. Acomposition comprising the product of reaction of ingredientscomprising melamine, formaldehyde and a diamino s-triazinylhydroxyphenyl-carbamyl-methyl sulfide.

19. A resinous composition comprising the product of reaction of (1) a.partial condensation product of ingredients comprising urea, formaldehdeand diamino s-triazinyl para-hydroxyphenyl-carbamyl-methyl sulfide, and(2) a. chlorinated acetamide.

20. The method of preparing new condensation products which comprisesefiecting reaction between ingredients comprising an aldehyde and acompound corresponding to the general for mula where n represents aninteger and is at least 1 and not; more than 2, Z represents a member ofthe class consisting of oxygen and sulfur, Y represents a divalentcarbocyclic radical, and R represents a member of the class consistingof hydrogen and monovalent hydrocarbon and halohydrocarbon radicals.

GAETANO F. DALELIO.

CERTIFICATE OF CORRECTION. Patent No. 2,512,702. March 2, 191g.

GAETANO F. D AIELIO.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2,first column, line 70, for "beta" read betapage 14., first column, line22, before 'chloroacetamide" insert --the-; and second column, line 62,for "approx." read --(approx.-; page 5, first column, line 51, for 60.6read 60.0 and second column, line 70, for "ortho-hydroxyphenyl" readortho-hydroxyphenylpage 6, second column, line 66, strike out "the",second occurrence; page 7, first column, line 14.9, for "aboxe"read--above--;

page 8, first column, line 1, for "aminothiazole" read -aminotriazole;and second column, line 58, claim 10, for "or oxygen read -of oxygen--;and that the said Letters Patent should be read with this correctiontherein that the same may conform to the record of the case in thePatent Office.

Signed and sealed this 1st day of June, A. D. 1911.5.

Henry Van Arsdale (Seal) Acting Commissioner of Patents.

